New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

All-fiber,octave-spanning supercontinuum

We present an all-fiber supercontinuum source based on a passively mode-locked erbium fiber laser and a small-effective-area, germanium-doped silica fiber. The parallels between this system and the continuum generated in microstructured fibers with 800-nm pulses are discussed, and the role of dispersion is investigated experimentally. We construct a hybrid fiber by fusion splicing lengths of different-dispersion fiber together, generating more than an octave of bandwidth.     

Propagation of femtosecond pulses in large-mode-area, higher-order-mode fiber

We demonstrate propagation of 14 nJ femtosecond pulses through a large-mode-area, higher-order-mode (HOM) fiber with an effective area of 2100 microm2. The pulses propagate stably in the LP07 mode of the fiber through lengths as long as 12 m. The strongly chirped pulses exiting the amplifier fiber are dechirped by the high-order-mode fiber, resulting in pulses with a peak power of 61 kW after propagation in 5 m of the positive-dispersion fiber. A small amount of self-phase modulation is observed in the compressed pulses and is described well by a nonlinear Schr?dinger equation model that takes into account the measured effective area and dispersion of the HOM fiber.     

High-energy (nanojoule) femtosecond pulse delivery with record dispersion higher-order mode fiber

Delivery of high peak-power femtosecond pulses with fibers is constrained by nonlinear distortions accumulated during pulse propagation. We address this problem with a novel, to our knowledge, fiber schematic, where the pulse propagates in a small Aeff (18 microm2) but highly dispersive (record value of approximately -900 ps/nm km) medium, enabled by transmission in the LP02 mode of a few-mode fiber. The novel fiber yields a low dispersion-to-nonlinear-length ratio (due to its large dispersion) despite its small Aeff, hence enabling mitigation of nonlinearities. This enables fiber delivery of distortion-free <150 fs, approximately 1 nJ, and 840 nm pulses--an order-of-magnitude improvement over single-mode fibers of similar Aeff.     

Coherence of supercontinua generated by ultrashort pulses compressed in optical fibers

Femtosecond fiber lasers together with nonlinear fibers are compact, reliable, all-fiber supercontinuum sources. Maintaining an all-fiber configuration, however, necessitates pulse compression in an optical fiber, which can lead to nonlinearities for subhundred femtosecond, nanojoule pulses. In this work we show that using large-mode-area fibers for pulse compression mitigates the nonlinearity, resulting in compressed pulses with significantly reduced satellite pulses. Consequently, supercontinua generated with these pulses are shown to have as much as a 10 dB increase in coherence fringe contrast. By using a hybrid highly nonlinear fiber-photonic crystal fiber, the continuum can be extended to visible wavelengths while still maintaining high coherence.